JPS58222138A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. giving a film which is transparent and has excellent chemical resistance, etc., containing a plurality of multi-layer structures having a special tapered structure between an inner layer composed of a crosslinked elastomeric polymer layer and an outer layer composed of a resin layer having a specified glass transition temp. CONSTITUTION:A first thermoplastic resin compsn. is obtd. from 1-99pts.wt. multi-layer structure polymer and 99-1pts.wt. another multi-layer structure polymer. 1-99pts.wt. said first resin compsn. is blended with 99-1pts.wt. polymer selected from the following group ( I ) or (II), or mixtures thereof to obtain a second thermoplastic resin compsn. The group ( I ) consists of homopolymers of a monomer of formula (a), (b) or (c) (wherein X, Y are each H, Cl, CH3; Z is H, F; R is fluoroalkyl) and copolymers thereof. The group (II) consist of polycarbonates, thermoplastic polyesters and polyamides.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel acrylic thermoplastic resin composition that is transparent and highly flexible.

More specifically, it has a special Chi Bird structure between a crosslinked elastic polymer layer (inner layer) having a two-layer structure and a resin layer (outer layer) having a glass transition temperature (hereinafter abbreviated as T/) of 60° C. or higher. At least one type of multilayer structure polymer CI which is transparent and has excellent weather resistance, solvent resistance, stress whitening resistance, molding processability, etc. and cross-linked elasticity 1 are combined. (A transparent and highly flexible product obtained by blending the two types.)

Moreover, it is weather resistant, solvent resistant, and stress whitening resistant.

This invention relates to a novel acrylic thermoplastic resin composition that has excellent processability.

Acrylic resins, especially methyl methacrylate polymers, are known to have both excellent transparency and weather resistance, and are used in cast molded products.

Widely used for extrusion molded products. However, it is widely known that these methyl methacrylate polymers are generally hard and brittle, making them unsuitable as materials for films and sheets, and that they cannot be used in applications that require flexibility. It is.

For this reason, a number of attempts have been made to introduce certain rubber components into methyl methacrylate polymers with the aim of imparting toughness and flexibility, but these efforts have resulted in a significant decrease in weather resistance. This is an attempt to add toughness and flexibility without sacrificing the excellent characteristics of methyl methacrylate polymers, such as transparency and weather resistance. has not been successful.

Furthermore, from the viewpoint of materials for films and sheets, methyl methacrylate-based multilayer structure polymers containing acrylic rubber have been proposed.

However, most of these multilayer structure polymers sacrifice the inherent characteristics of methyl methacrylate polymers, such as transparency and weather resistance, in order to impart toughness and flexibility, which is unsatisfactory. It has not become a thing. Furthermore, these multilayered polymers have flexibility and toughness that are difficult to process (fluidity) due to limitations in their polymer structure.

Since these properties are contradictory to various properties such as weather resistance and solvent resistance, there is a limit to the ability to impart flexibility without sacrificing these properties. For this reason, even if it is possible to provide a degree of flexibility and toughness that is not difficult to handle as a material for films and sheets, the current situation is that it cannot be used for applications that require even greater flexibility. .

In view of the current situation, the inventors of the present invention have made a clear decision.

As a result of intensive study to obtain an acrylic polymer that has excellent stress whitening resistance and solvent resistance without sacrificing weather resistance and processability, and also has arbitrary flexibility, we have developed an acrylic polymer with a two-layer structure. Between a crosslinked elastic polymer layer (inner layer) mainly composed of acrylate and a resin layer (outer layer) mainly composed of alkyl methacrylate with T/ of 60°C or more, alkyl acrylate and alkyl methacrylate are mainly composed. It has a basic polymer structure including at least one intermediate layer in which the amount of alkyl acrylate monotonically decreases from the crosslinked elastic polymer layer to the resin layer,
Furthermore, the resin layer is transparent and has excellent weather resistance, solvent resistance, stress resistance (5), whitening property, processability, etc. [at least one of at least one of 11]. It is a multi-N polymer with a crosslinked elastic material as a core and a resin layer as an outer layer, and the crosslinked elastic polymer layer is in a predominant amount with respect to the resin layer.

The present invention has been accomplished by discovering that the object of the present invention can be achieved by blending at least one transparent and particularly flexible multilayer polymer.

The gist of the present invention is to provide a first thermoplastic resin composition comprising 1 to 99 parts by weight of at least one kind of multilayer structure polymer [II] and 99 to 1 part by weight of at least one kind of multilayer structure polymer [■]. Invention and Resin Blends 1 to 99 parts by weight of at least one kind of multilayer structure polymer [I] and as little as 99 to 1 part by weight of multilayer structure polymer [111]
99 parts by weight of at least one polymer selected from the following group (1) or (11), or a mixture of at least one polymer selected from each of the groups (:) and (II). Thermoplastic resin composition r, c consisting of 1 part by weight
According to the second invention. □(6) Polymer (1): A homopolymer of a monomer having the following general formula (a), (b) or ta+v, or a copolymer consisting of two or more of these monomers.

CH,=CXY -------(a) However, in the formula, X and Y are H, C13, F, Br, CH,.

C0OH, C00CH,,CN, 0COCH,,C
,H,.

Alkoxy group, 0CCHs, 80. Either H.

CF,=CFZ ・--(b) However, in the formula, Z H
, F, ce, CF, tD are Izureka.

CH, =C-C00R--・--・--(e) Castle However, in the formula, R is a fluoroalkyl group.

Polymer (il): Polycarbonate, thermoplastic polyester.

polyamide.

In the present invention, the multilayer structure polymer [I] and the multilayer structure polymer CUE have the following polymer structures.

Multilayer structure 1 combination [I]: 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (AI).

0 to 20 parts by weight of a monomer having a copolymerizable double bond (A).

0 to 10 parts by weight of polyfunctional monomer (As).

0.1 per 100 parts by weight of the total amount of (A1) to (A,)
From the composition of ~5 parts by weight of the grafting agent, the innermost layer polymer (A) accounts for 5 to 35% by weight in the multilayer structure polymer [13].

Alkyl acrylate containing 7 alkyl groups having 1 to 8 carbon atoms and having a Mt part of 80 to 100'' (Bl).

0 to 20 parts by weight of monomers with copolymerizable double bonds (Cut).

0 to 10 parts by weight of polyfunctional monomer (Bs).

(Bl) ~ (0.1 to 100 parts by weight of the total amount of Bli)
5 parts by weight of a graft cross-agent.

A crosslinked elastic polymer (B) that accounts for 10 to 45% by weight in the multilayer structure polymer [I].

51 to 100 parts by weight of alkyl methacrylate (CI) having 1 to 4 carbon atoms.

The composition consists of 0 to 491 parts by weight of a copolymerizable double bond monomer (C8) and has a low TI (both at 60°C).

The proportion in the multilayer structure polymer CD is 30 to 80% by weight
The outermost layer polymer (C) is the basic structural unit, and the 'N polymer (B) layer and the polymer (C)
An alkyl acrylate (DI) having 10 to 90 parts by weight of an alkyl group having 1 to 8 carbon atoms as an intermediate layer (D) between the layers.

Alkyl methacrylate containing 90 to 10 parts by weight of alkyl groups having 1 to 4 carbon atoms (D,).

0 to 20 parts by weight of a monomer (DI) having copolymerizable double bonds.

0 to 10 parts by weight of polyfunctional monomer (D4).

0.1 per 100 parts by weight of the total amount of (D,) to (D4)
~5 parts by weight of the graft cross-agent, such that the amount of alkyl acrylate in the middle (9) and interlayer (D) monotonically decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C). Intermediate layer (D) A multilayer structure polymer [1] having at least one layer of yx and having a gel content of at least 50%.

Multilayer structure polymer [■]: 60 to 100 parts by weight of alkyl acrylate (A'1) having an alkyl group having 8 or less carbon atoms.

0 to 40 parts by weight of a monomer (A'2) having a double bond capable of co-merging.

0 to 10 parts by weight of polyfunctional monomer (A/, ).

0.1 per 100 parts by weight of the total amount of (Ni1) to (Ni,)
The gel content is 60% by weight or more and the swelling degree is 15 or less, consisting of a composition of ~5N parts of the grafting cross-agent.

and the amount in the polymer [■] is 40 to 80% by weight
and an alkyl methacrylate having 60 to 100 parts by weight of an alkyl group having 4 or less carbon atoms (B'l).

The outermost layer consists of a monomer (B;) (10) having a copolymerizable double bond of 0 to 40 parts, and the amount occupied in the polymer Cnl is 10 to 60 parts. Combine (B')! The basic structural unit, if desired, can be combined with a polymer layer (B'
) Alkyl methacrylate <C;) having 10 to 90'N parts of an alkyl group having 4 or less carbon atoms between the layers.

10-90! Alkyl acrylate (C;) having a quantity of alkyl groups having 8 or less carbon atoms.

θ~20! A compound having a double bond that can be co-located with a number of parts ((:l).

0 to 10 parts by weight of polyfunctional monomer (C;).

0.1 per 100 parts by weight of the total amount of (C;) to (C;)
A multilayer structure polymer [■
].

The features of this invention are transparency and weather resistance.

Excellent stress whitening resistance, solvent resistance and processability□,,,
U□ska. 8 Ohata t□technical. □1 Although inferior, it is extremely flexible and transparent.

By blending with a multilayer polymer with excellent weather resistance [...], a thermoplastic resin composition with excellent transparency, weather resistance, flexibility, and processability that could not be obtained with conventional multilayer polymers alone was obtained. It is a point.

The basic polymer structure of the multilayer structure polymer [1] used in the present invention has the following characteristics. That is, (1) the crosslinked elastic polymer (B) had a two-layer elastic structure including the innermost layer polymer (A) as an inner layer.

(2) The T/Y of the outermost layer 1, which is a resin layer, is set at 60° C. or higher.

(3) Between the crosslinked elastic polymer layer and the outermost polymer layer, the intermediate layer is arranged in a manner such that the ratio of alkyl acrylate monotonically decreases from the crosslinked elastic polymer layer to the outermost polymer layer. thing.

(4) Chemical graft crossover using the above-mentioned interlayer graft crossover agents.

(5) The gel content of the final polymer was kept small (to a total of 5°).

From satisfying all of these requirements, the multilayer structure polymer [I] has excellent transparency, weather resistance, stress whitening resistance, and solvent resistance, which are the basic characteristics of the multilayer structure polymer composition used in the present invention. Satisfaction can only be achieved for the first time, and if even one of these requirements is missing, nothing can be achieved.

In particular, the multilayer structure 1 combination [i] in the present invention is characterized in that the crosslinked elastic polymer layer is composed of a two-layer elastic structure including an innermost layer polymer as an inner layer.

In general, acrylic rubber has excellent weather resistance compared to diene rubber, etc., but elastic recovery is slow (deformation due to stress is large, and rubber efficiency is low. In other words, it has excellent weather resistance while maintaining the above-mentioned resistance. In order to provide properties such as solvent resistance and water whitening resistance, there is a limit to the elastic body structure consisting of only one layer obtained by conventional one-stage polymerization.

In order to solve these drawbacks, the multilayer structure polymer CD used in the present invention has the innermost layer polymer (A) yx present in the core of the crosslinked elastic polymer (13) body (B). The presence of the inner layer polymer (A) polydispersively relieves the stress concentrated on the crosslinked elastic polymer (B) layer when the stress Yb increases, and as a result, the incidence of microvoids increases and the apparent stress is reduced. It provides excellent impact resistance even without whitening.

In the case of the multilayer structure polymer [1], the ratio of the resin layer is set to be approximately the same amount or more than that of the crosslinked elastic polymer layer.

Although it lacks some flexibility, its weather resistance and solvent resistance are even better.

Furthermore, by controlling the gel content of the final polymer to 80% or less, it also has excellent processability.

The argyl acrylate having an alkyl group having 1 to 8 carbon atoms and constituting the innermost layer polymer (A)' of the multilayer structure polymer [1) may be either linear or bibranched, and may be methyl acrylate, ethyl acrylate, Propyl acrylate, butyl acrylate (14)-, 2-ethylhexyl acrylate, n-octyl acrylate, etc. are used alone or in combination, but TP
A lower one is more preferable.

The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be linear or bibranched, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl methacrylate, etc. are used alone or in combination. These alkyl (meth)acrylates (
AI) is used in the range of 8O-1003iit parts.

In addition, it is most preferable that these alkyl (meth)acrylates are then used uniformly in all multi-layer layers, but depending on the final purpose, two or more types of single substances may be mixed, or different types of (meth)acrylates may be used. Good too.

Also, a monomer having a copolymerizable double bond (Aρ is lower alkyl acrylate, lower alkoxy, etc.).

Acrylic monomers such as acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid are preferred, and 0 to 20'! [Used within the scope of the section. Others (A) Styrene, alkyl-substituted styrene, acrylonitrile, methacrylaterile, etc. can be used within a range not exceeding 20% by weight in X minutes.

Furthermore, the polyfunctional monomer (A) is preferably an alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4 butylene glycol dimethacrylate, and propylene glycol dimethacrylate, and divinylbenzene.

Polyvinylbenzenes such as trivinylbenzene and hyalkylene glycol diacrylates can also be used.

These monomers act effectively to bridge the layer itself, but do not act on bonding between layers with other layers. Polyfunctional monomers (A, ) is fairly stable even if it is not used at all as long as the grafting cross-agent is present.

Although it can be used as desired depending on the required physical properties, the amount used is in the range of 0 to 100 parts by weight.

On the other hand, the grafting agent used is a copolymerizable allyl, methallyl or crotyl ester of an α,β-unsaturated carboxylic acid or dicarboxylic acid, preferably a 71J ester of acrylic acid, methacrylic acid, maleic acid and fumaric acid, especially allyl methacrylate. has excellent effects. Triallyl cyanurate, triallyl isocyanurate and the like can also be effectively used. Such graft cross-agents are chemically bonded primarily because the conjugated unsaturated bonds of their esters react much faster than allyl, methallyl, or crotyl groups. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group acts effectively during the polymerization of the next layer to provide a graft bond between two adjacent layers.

The amount of graft cross-agent used is extremely important.
) to (A, ) are used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount. If the amount used is less than 0.1 part by weight, the effective amount of graft bonding will be small and the bonding between the layers will be insufficient (17). In addition, if the amount used exceeds 5 parts by weight, the amount of reaction with the crosslinked elastic polymer (B) polymerized in the second stage becomes large, resulting in a two-layer crosslinked structure consisting of the polymer (A) and the polymer (B). This leads to a decrease in the elasticity of the elastic body.

The innermost N11L union (A) is the graft-active layer.

The TP is appropriately set depending on the physical properties required of the final polymer. Further, it is generally advantageous in terms of quality that the crosslinking density is the same as or even higher than that of the crosslinked elastic polymer (B). Note that the innermost layer polymer (A) and the crosslinked elastic polymer (B
) may have the same composition, but it is important that it has a knee elastic body structure through two-stage polymerization, and that the catalyst amount, crosslinking density, etc. are set according to the weight. It is advantageous that the coalescence (A) is higher.

Considering the initial polymerizability, the presence of the innermost layer polymer (A) is extremely important in order to obtain a stable multilayer structured polymer, and generally a large amount of catalyst is added to the innermost layer of each polymer layer.

(18) The use of a grafting cross-agent is essential for effectively synthesizing a two-layer elastic structure that is chemically bonded to the crosslinked elastic polymer (B) formed in the second stage. . Without this graft bond, the two-layer elastomer structure would easily undergo phase destruction during melt molding, resulting in lower rubber efficiency and failing to exhibit the desired excellent weather resistance, stress whitening resistance, etc.

The content of the innermost layer polymer (A) in the multilayer structure polymer [13] is 5 to 35% by weight, preferably 5 to 15% by weight, and is preferably lower than the content of the crosslinked elastic polymer (B).

Next, the multilayer structure polymer [■] is composed of a cross-linked elastic polymer (
B) is a main component that gives rubber elasticity to the aggregate CI), and is an alkyl acrylate containing 80 to 100 parts by weight of an alkyl group having 1 to 8 carbon atoms (B), 0 to 20
Parts by weight of copolymerizable di'li.

Monomer having a double bond (BJ, 0.1 to 5 Nt parts per 100 parts by weight of the total amount of polyfunctional monomers (B,) and (B1) to (B,) with o to 10 folds) is composed of a graft cross-agent.

As the alkyl acrylate (B1) having an alkyl group having 1 to 8 carbon atoms, the alkyl acrylates exemplified in (A1) above can be used alone or in combination, but T/
A lower one is more preferable.

As the monomer (B2) having a copolymerizable double bond, lower alkyl methacrylate is most preferable, and other (
The same monomers as exemplified in A,) are used. Further, as the polyfunctional monomer (BA) and graft cross-agent, those exemplified in the case of the innermost polymer (A) can be used.

T/ of the crosslinked elastic polymer (B) alone is 0°C or less.

Preferably, the temperature is -30°C or lower to provide good physical properties.

The content of the crosslinked elastic polymer (B) in the multilayer structure polymer CD is preferably in the range of 10 to 45% by weight, and is preferably higher than the content of the innermost layer polymer (A).

In this way, the innermost non-polymer (A) and the crosslinked elastic polymer (B
) has a two-layer cross-linked elastic body structure in which the two layers are graft-bonded, making it possible to simultaneously satisfy various properties that could not be achieved with conventional mono-based rubbers. .

In order to obtain excellent physical properties, it is necessary for this two-layer crosslinked elastic body to have a gel content of 85% by weight or more and a swelling degree of 3 to 13, as determined by the following measurement method. .

(Measurement method for gel content and swelling degree) A predetermined amount of the two-layer crosslinked elastic material was sampled according to JIS K-6388, and methyl ethyl ketone (hereinafter referred to as M
It is abbreviated as EK. ), immerse it in swollen water, pull it up, wipe off the adhered MEK, measure its weight, then dry and remove the MEK in a vacuum dryer, read the absolute dry weight that has reached a constant weight, and calculate it using the following formula.

Generally, the degree of polymerization of the crosslinked elastic polymer (B) should be as high as possible to impart high impact strength to the final polymer21). - Innermost layer polymer (A), which is the most important VC, is not limited to this, but rather uses a large amount of catalyst to stabilize the initial polymerization including particle formation, and also uses a large amount of graft active groups. However, the performance as a two-layer crosslinked elastic body tends to be good.

Furthermore, the outermost layer 1 (C) constituting the multilayer structure polymer [I] is involved in distributing moldability, mechanical properties, etc. to the polymer [I]; C1
) Components include the alkyl methacrylates exemplified in the component (AI) described above, lower alkyl acrylate 7 as the C component, and monomers exemplified as the C component (A2), each singly or in combination. The component (C1) is used in a range of 51 to 100 parts by weight, and the component (C2) is used in a range of 0 to 49 parts by weight.

Note that T/ of the outermost layer polymer (C) alone needs to be 60° C. or higher, preferably 80° C. or higher in order to obtain excellent physical properties. If T/ of the polymer (C) alone is less than 60°C, the gel content of the final polymer [I] to be described later may be 5.
0% weight ratio or higher (22) Excellent physical properties% 7. C.

The content of the outermost layer polymer (C) in the multi-1-structure polymer CD is 30 to 5 oit%, preferably 45 to 65 oit%.

The multilayer structure polymer (1) used in the present invention includes the innermost layer polymer (A), the crosslinked elastic polymer (B), and the outermost layer polymer (
C) 'Y basic structural unit, and between the polymer (B) layer and the polymer (C) layer, 10 to 90 parts by weight of 1 to 1 carbon atoms.
Alkyl acrylate (D,) having 8 alkyl groups
, 90~10i1f'! 1 part of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms) (D2),
0 to 20 parts by weight of a copolymerizable monomer having double bonds (Ds)-o to 10 parts by weight of a polyfunctional monomer (D4),
0.0% per 100 parts by weight of the total amount of (DI) to (D4).
An intermediate layer (D) consisting of a composition of 1 to 5 parts by weight of graft cross-agent.

The amount of alkyl acrylate in the intermediate layer (D) is the same as that of the polymer (
At least one layer is arranged so as to monotonically decrease from layer B to the layer of polymer (C). Here, the components (n+) to (D4) and the graft cross-agent are each (
Bl), (CI), (At), (A3) and the graft cross-agent used in innermost layer 1 coalescence (A). The grafting agent used in the intermediate layer (D) is essential for closely bonding each polymer layer and obtaining excellent physical properties.

The content of each intermediate layer (D) in the multilayer structure polymer [1) is 5 to 35% by weight, preferably 5 to 25% by weight,
If it is less than 5% by weight, the function as an intermediate layer will be lost, and if it exceeds 35% by weight, the final polymer will lose its balance, which is not preferable.

Furthermore, the multilayer structure polymer [I] used in the present invention has a gel content of at least 50% by weight, preferably as little as 6% by weight.
It is 0% by weight, and only when this is satisfied together with the above-mentioned special structure does it provide excellent properties such as stress whitening resistance, impact resistance, solvent resistance, and water whitening resistance. In this case, the gel content refers to the two-layer crosslinked elastic body itself, the intermediate layer (D), the outermost layer,
.

It contains a graft component of the outer layer polymer (C) to the crosslinked elastic body, and the gel content here refers to the multilayer structure polymer [
Prepare an INi% MEK solution of [I], leave it overnight at 25°C, and then centrifuge at 1600 Or, p, m, 90
It is the weight percent of insoluble matter after centrifugation for one minute. The component of the gel content is the added weight of the two-layer crosslinked elastic body and the grafted chain, and it can also be replaced by the grafting ratio, but in the present invention, since the polymer [1) has a special structure, the gel content is This was used as a guideline for the amount of grafting.

From the point of view of solvent resistance, the higher the gel content, the more advantageous it is, but from the point of view of easy moldability, the presence of a certain amount or more of free polymer is necessary, so the upper limit of the gel content is about 80% by weight. is preferred.

The most suitable method for producing the multilayer structure polymer [I] is a sequential multistage polymerization method using an emulsion polymerization method, but it is not particularly limited thereto.1 For example, after emulsion polymerization, the outer layer polymer (C) It can also be carried out by the emulsion suspension Togane method, in which the polymerization is converted into a suspension polymerization system. There are no particular restrictions on the surfactant, catalyst, etc. used during production. There is also no particular limit to the particle size of the final polymer (25), but particles in the range of about 800 to 20,001 exhibit the most balanced physical properties. Additives such as antioxidants and lubricants are added to the emulsified latex of the multilayered polymer as necessary and salted out.

Next, the multilayer structure polymer (l[] used in the present invention will be explained.

Innermost layer polymer (A') constituting the multilayer structure polymer [■]
imparts flexibility and toughness to the polymer [11].

This imparts flexibility and toughness to the final blended composition. The polymer (A') is an alkyl acrylate having an alkyl group having 8 or less carbon atoms and forming a Y shadow.
) As (A'l), at least one of methyl acrylate, ethyl acrylate, propyl acrylate, phthyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc. is used in an amount of 60 to 100 parts by weight. The lower the T/ of the homopolymer of these monomers, the more advantageous.

The monomer (2) having a double bond that can be copolymerized is one that can be copolymerized (26) with the alkyl acrylate (A'l), such as lower alkyl methacrylate, lower alkoxy acrylate, cyanethyl acrylate, acrylamide, (Meth)acrylic acid-conducting conductors such as acrylic acid and methacrylic acid are preferred, and other examples include styrene, alkyl-substituted styrene, acrylonitrile, and methalylonitrile, which are used in the range of O to 40i.

The polyfunctional monomer (2) is used in a range of 0 to 10 parts by weight, specifically ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene. Glycol dimethacrylate and the like are preferred, and further examples include divinylbenzene and alkylene glycol diacrylate.

The total amount of each graft cross-fertilizing agent is 100
0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight
It is used in the range of parts by weight, and a specific example is comonomorphic α
, β-unsaturated monocarboxylic acid or dicarboxylic acid allyl ester, methalyl ester, crotyl ester, hydrarylyl cyanurate, triallyl isocyanurate, and the like. Acrylic acid is an allyl ester.

Examples include allyl esters such as methacrylic acid, maleic acid, fumaric acid and itaconic acid, with allyl methacrylate showing particularly excellent effects. The amount of graft cross-agent used is 0.
If it is less than 1 part by weight, the effective amount of graft bonding is too small, so that layer destruction easily occurs during molding of the final polymer, resulting in a significant decrease in transparency, etc. Moreover, if the amount exceeds 5 parts by weight, the elasticity is particularly reduced.

Flexibility 9: Cannot impart sufficient toughness.

The amount of the innermost layer polymer (A) in the multilayer structure polymer [11] is 40 to 80% by weight. Amounts less than 400 parts by weight do not provide the desired flexibility and toughness to the final multilayer polymer blend composition. 80 again
If the amount exceeds 10% by weight, the multilayer structure polymer [■] will not only become rubbery and difficult to handle, but also have various physical properties such as transparency significantly reduced. The innermost layer polymer (A')' made of a crosslinked elastic material of acrylic rubber can have a two-stage structure or a three-stage structure, if necessary.

Furthermore, in addition to the above, the innermost layer polymer has preferable ranges in terms of gel content, swelling degree, particle diameter, etc. In particular, regarding gel content and swelling degree, the above-mentioned multilayer structure polymer [
The gel content determined by the measuring method described in the crosslinked elasticity 1 combination of [I] is 60% by weight or more, preferably 801M
%that's all.

It is necessary that the degree of swelling is 15 or less, preferably in the range of 3 to 15.

The particle size of the innermost layer polymer is 500 to 500.
If it is within the range of 0A, the transparency and rigidity stress whitening property of the final multilayer structure polymer [■] will not be significantly reduced.

Next, as the acrylic multilayer structure polymer [ID'& alkyl methacrylate having an alkyl group having 4 or less carbon atoms forming the constituent outermost layer polymer (B') (B',), methyl methacrylate- At least one of ethyl methacrylate (29), probyl methacrylate, butyl methacrylate, etc. is used in an amount of 60 to 100 parts, with methyl methacrylate being particularly preferred.

Examples of the monomer (B;) having a copolymerizable double bond include alkyl acrylates having an argyl group having 8 or less carbon atoms, as well as those shown in component (2) above.

These components (B'2) are used in an amount of 0 to 40 parts by weight.

The amount of the outermost layer polymer (B') in the multilayer structure polymer [11] is 10 to 60% by weight. If the amount is less than 100 parts by weight, a stable polymer cannot be obtained from the viewpoint of polymerization and coagulation operations. Moreover, when the amount exceeds 60% by weight, the content of the innermost layer polymer becomes small and the desired elasticity is obtained.

Incidentally, during the polymerization of the outermost layer polymer (B'), it is possible to control the degree of polymerization by using a chain transfer agent or the like, and this is often preferable.

The multilayer structure polymer [■] used in the present invention has the above-mentioned innermost layer polymer (A') and outermost layer polymer (B') as basic (30) structural units. 1 Alkylacryne (C;) having an alkyl group of from 10 to 90 M parts of a carbon moiety between the polymer (A') layer and the polymer (B') layer, 90 to 1ON.

Alkyl acrylate (C;) having an alkyl group having a carbon number of 8 or less in the lower part, 0 to 20 parts by weight of a monomer (Cs) having a copolymerizable double bond, o to 10 parts by weight The total amount of polyfunctional monomers (CL), (C;) to (C;) is 100! It is possible for the intermediate layer (C') to have a composition of 0.1 to 5 parts by weight of a graft cross-agent based on parts of (cr) to (C; )
The same components and graft cross-agents as those used in the polymers (A') and (B') are used.

The amount of the intermediate layer (C') in the multilayer structure polymer [■] is suitably 50% by weight or less, and if it exceeds 50% by weight, it is not preferable because the overall final polymer and the balance will be disturbed.

The multilayer structure polymer [■] can also be easily obtained by a sequential multistage polymerization method using a conventional emulsion polymerization method. That is, the innermost layer polymer (
) is first obtained by an emulsion polymerization method, and then the polymer (A')
Polymerize the next layer in the presence of .

In this case, no emulsifier is added to form new T, C polymer particles. Thereafter, repeat this step (9 times) to complete the polymerization of the multilayer structure polymer [11].

Emulsifiers, catalysts, coagulants, etc. used during polymerization are not regulated by percentage. Note that an emulsion suspension polymerization method in which only the outermost layer polymer (B') is converted to suspension polymerization after emulsion polymerization is also an advantageous method.

The blending ratio of the multilayer structure polymer [I] and the multilayer structure polymer [11] is within the range of 1 to 99 parts by weight for the multilayer structure polymer [I] and 99 to 1 part by weight for the multilayer structure polymer [■]. It can be set arbitrarily depending on the desired flexibility and workability.

When carrying out the present invention, the multilayer structure polymer CII and the multilayer structure polymer [11]'a' may be used alone, or two or more of each of the I7>polymers may be combined in the above blending ratio range. used.

The multilayer structure polymer [I] and the multilayer structure polymer [11] can be blended by a conventional method such as using a 7-shell mixer into each powder, or after mixing each latex. It is also not possible to blend them by performing treatments such as salting out.

Also, when blending multilayer structure polymer CI] and multilayer structure 1 combination [11], an ultraviolet absorber and an antioxidant.

General additives such as pigments and lubricants can also be added, and in particular, by adding an ultraviolet absorber, a resin composition with even better weather resistance can be obtained.

At least one polymer selected from the group of polymers (1) or (11) described above in 1 to 99 parts by weight of a resin composition containing the multilayer structure polymers of the present invention in the above proportions,
Alternatively, 99 to 1 part by weight of a mixture of at least one polymer selected from each of the groups of polymers (1) and (11) can be added.

The multilayer structure polymer [I] used in the present invention is cross-linked with an alkyl acrylate as a main component in the presence of the innermost (33) NN polymer (A), which has a specific alkyl acrylate or alkyl methacrylate as a main component, as described above. Polymerize the elastic polymer (B).

T/ with alkyl acrylate as the main component as the outermost layer
An outermost polymer (C) having a temperature of at least 60° C. is disposed between the polymer (B) layer and the polymer (C) layer, and the amount of alkyl acrylate is increased from the polymer (B) layer to the polymer (C) layer. Combine (C)
A multilayer comprising an intermediate layer (D) that monotonically decreases toward the layers, in which each polymer layer other than the polymer (C) layer is effectively graft-bonded, and has a specific gel content. Because it has a polymer structure, it has excellent transparency when blended with other compatible thermoplastic resins with different refractive indexes as an essential component.

This makes it possible to create a resin composition that has no or very little stress whitening property.

Transparency, stress whitening resistance, and weather resistance, especially when blended with methyl methacrylate resin.

A resin composition with excellent impact resistance can be obtained.

It is surprising that the stress whitening property of the polymer blend system is extremely small. This is due to the special structure of the multilayer polymer [I], and is compared with the conventional one. This cannot be predicted from the method of introducing the rubber component.

In addition, when blended with vinyl chloride resin, polystyrene, AS resin, or polycarbonate resin, the blend composition of multilayer structure polymers [1] and [■] has a kind of weather resistance.
Acts as an impact modifier, significantly improving weather resistance and impact resistance.

Furthermore, blend compositions with polyvinyrizo/fluoride/vinyrizo/fluoride are excellent in various properties such as weather resistance, transparency, stress whitening resistance, chemical resistance, toughness, moldability, etc. Part and multilayer structure polymer [I] and [1
A resin composition containing 50 to 99 parts by weight of the blended composition of 1) is excellent as a material for film molding, and is transparent and tough, and has excellent weather resistance, stress whitening resistance, chemical resistance, etc. Give Z. Such a film can easily impart weather resistance and a design effect by laminating it on the surface of an ordinary molded article, and has extremely high commercial value.

The present invention will be specifically explained below using Examples.

In addition, both "parts" and "%" in the examples are "parts by weight."
and “parts by weight”.

Furthermore, the abbreviations used in the examples are as follows.

MMA: Methyl methacrylate MA: Methyl acrylate Bu, A: Butyl acrylate 2EHA:
2-ethylhexyl acrylate St: Styrene BD: 1,3-butylene dimethacrylate AMA
: Allyl methacrylate CHP : Cumene hydroperoxide SFS : Sodium formaldehyde sulfosylate The TP of each polymer layer used in the examples is FOX, which is commonly known from the TP value described in the polymer handbook, for example. It was calculated using the formula.

Example 1 (1) Production of multilayer structure polymer CI'l 250 parts of ion-exchanged water, 2 parts of sulfosuccinic acid ester soda salt, and 80.05 parts of 5F were placed in a polymerization vessel equipped with a cooler and stirred under a nitrogen stream. MMA 1.6 part, BuAS part,
A mixture consisting of 4 parts BDo, 1 part AMAo, and 4 parts CHPo was charged. After raising the temperature to 70°C, the reaction was continued for 30 minutes to complete polymerization of the innermost layer polymer (A). followed by 5 parts of MMA1, 5 parts of BuA, 1 part of BD, 25 parts of AMAo, and 0 to the monomer mixture of these.
．． The mixture containing 05% C) IP was added over 60 minutes and held for an additional 60 minutes to form the polymer (A),
A two-layer crosslinked elastic body consisting of two layers (B) was polymerized. The degree of swelling of the thus obtained two-layer crosslinked elastic body in MEK (37) was 1 (1,0), and the gel content was 90%.

Next is 5 parts of MMA, which corresponds to the middle layer (D).

A mixture consisting of 5 parts of BuA and 1 part of AMAo was added for 10 minutes to polymerize, and finally a mixture of 52.25 parts of MMA and 2.75 parts of BuA was similarly polymerized to form the outermost layer polymer (C). Combination 1-(1)'Y was obtained. However, when polymerizing the intermediate layer (D) and the outermost layer (C), CHP'&
Using.

Similarly, a multilayer structure polymer [:I-(213~[1-(
511 and comparative polymers (ill (2), (31) were polymerized.

In all cases, the final particle size was within the range of 1000 to 1500 A. These polymer latexes were salted out according to a conventional method, washed and dehydrated, and then dried to obtain dry powder.

Their compositions and physical properties are shown in Table 1.

(38) (2) Production of multilayer structure polymer El) A multilayer structure polymer having the structure shown in Table 2 was prepared using the same emulsion sequential multistage polymerization method as shown in the production of multilayer structure polymer CI). Coalescing [11-+1)) to [I[-(4t) and comparative polymer (4)] were polymerized.

The particle diameters of the obtained polymers were all 1000 to 2000.
It was within the range of A.

These polymer latexes were also salted out according to a conventional method, washed, dehydrated, and dried to obtain dry powder.

Their compositions and physical properties are shown in Table 2.

(40) (4]) (3) Production and evaluation of resin compositions Table 3
Blend in the proportions shown in and add 2 parts of ultraviolet absorber (
Tinuvin P (trade name, manufactured by Chinoku Geigy) was added, mixed well, and pelletized at 4% extrusion.

The obtained Beretton was dried at 70° C. for a day and night, and then a molding processability test was conducted using an injection molding machine. The results are also shown in Table 3. The criteria for determining moldability are as follows.

<Moldability evaluation criteria> ○: Can be easily molded with an injection molding machine.

△: Barely possible to mold with an injection molding machine.゛×: Difficult to mold with an injection molding machine.

Furthermore, using the same pellet, the thickness was 250 mm using the T-die method.
A sheet of μ was formed. The transparency (total light transmittance and haze value) of the samples that could be molded into good sheets was evaluated based on JIS K6714. In addition, the tensile modulus was measured as a measure of flexibility. For samples in which good strength was not obtained, the tensile modulus was not measured, and the transparency was evaluated by visual judgment.

In addition, the well-formed sheet was subjected to an accelerated exposure test for 3000 hours using a Sunshine Weather-Ometer, and the retention rate of elongation at break was determined from measurements of tensile elongation at break before and after the exposure, which was used as a measure of weather resistance. These results are also shown in Table 3.

In addition, the multilayer structure polymer CI-(111~1-(511°[
11-+1)) to [IIl, -(411) and comparative polymers (1) to (4) were blended in the proportions shown in Table 4, and the same evaluation was conducted.The evaluation results are also shown in Table 4. Ta.

It can be seen that all the products of the present invention have excellent transparency, weather resistance, and moldability, and have appropriate flexibility.

In addition, ratio (1) to ratio (41 is comparative polymer (1) to
Comparative polymer (4) is shown.

(43) Table 3 (44) (45) Example 2 Multilayer structure polymer [1-(t))70 synthesized in Example 1
Resin composition (Inventive Example (21) 50 parts'4 MMA/
MA copolymer (MMA/MA = 99/1 stacking ratio.

1 ap/c=0.60 (measured in a solution with a concentration of 0,10//di)) was blended with 50 parts using a Henschel mixer, and then pelletized using an extruder.

The obtained pellets were dried at 80°C day and night.

A sheet of 0.5 mm thick was formed using a T-die.

This blended polymer had good sheet formability, and a sheet with excellent transparency, gloss, etc. was obtained. Furthermore, using the same pellet, an injection molded plate with a thickness of 2 mm was obtained without injection molding. The total light transmittance and Dynstadt impact strength of the obtained molded plate were measured. Total light transmittance is 91%
, Dynstadt impact strength is 34 kllcm/
cm'' as well as extremely good values.

Further, the above-mentioned molded plate was subjected to an accelerated exposure test for 3000 hours using a Sunshine Weather-Ometer, and the gloss retention rate was measured. The gloss retention rate was extremely high at 92%, indicating that the product of the present invention also has excellent weather resistance.

Example 3 60 parts of the multilayer structure polymer Cl-11 synthesized in Example 1, 30 parts of the multilayer structure polymer [1L-(21)] and xo part of polyvinylidene fluoride (trade name: Kynar 500°, manufactured by Pennwalt) After blending using a shell mixer, the mixture was pelletized using a screw extruder. The obtained pellet was formed into a film with a thickness of 80 μm by an inflation method.

Tensile strength and elongation (JISz170
-2) and haze value (based on ASTM-D1003-61) were measured. Tensile modulus 7.5×10 kf/cm
2+ breaking strength 335 ky/cx”, breaking elongation 19
0% and haze value of 5.1%, both of which are extremely good. '□ Also, the obtained film was bonded to a galvanized 0.5 mm cold-rolled steel plate using an adhesive, and this bonded sample was subjected to a DuPont impact test (Tip R1, = T I / T, load 1 (lkl, drop). Height g50cm, temperature 2
(conducted at 0°C). No cracks showing whitening were observed in the impacted area.

Further, the film was subjected to an accelerated exposure test for 3000 hours using a sunshine weatherometer, and the tensile strength and elongation of the exposed sample was measured. The tensile elongation retention rate of the sample after exposure (the elongation of the unexposed product, expressed as iloO%; a measure of weather resistance) was 89 inches, and the product of the present invention also has excellent weather resistance. It was shown that

Patent applicant: Mitsubishi Rayon Co., Ltd. (48)

Claims (1)

[Claims] l. At least one kind of multilayer structure polymer [1] 1 to 99
Low amount of heavy food parts and multi-layer structure polymer [11] (both type 99
~1 part by weight of a thermoplastic resin composition. 2. Low amount of multilayer structure polymer [I] (both 1 to 99 parts by weight of one type and 99 to 99 parts of at least one type of multilayer structure polymer [1])
1 to 99 parts by weight of a resin blend consisting of 1 to 99 parts by weight of at least one polymer selected from the following group (1) or (11), or each of the groups (1) and (11). A thermoplastic resin composition comprising 99 to 1 part by weight of a mixture of at least one selected polymer. Polymer (1): A homopolymer of a monomer having the following general formula (a), (b) or (a)'l, or a copolymer consisting of two or more of these monomers. CH, = CXY = (a) where X,
YHaH, Ce, F, Br. CH8,C0OH,C00CH,,CN,OCOC
H3°C, HII, alkoxy group, 0CCH,, 8
03H. CF ==CFZ ・・・・・・・・・ (b)
Gobutashishikichu Z&'! H, F, C10, CF, 17)
It's a chair. However, in the formula, R is a fluoroalkyl group. Polymer (Il): polycarbonate, thermoplastic polyester. polyamide.